Stabilization of organic compounds



No Drawing. Application December 28, 1954,

. Serial No. 478,199:

12 Claims. (c1. 90-163) This is acontinuation-in-part of our copendingapplication Serial No. 394,518, filed November 25,1953, and

relates to the stabilization of organic compounds which tend todeteriorate in storage or in use due to oxidation or other reactions.

The novel method of the present invention may be utilized for thestabilization of various organic materials United States Patent whichare unstable in storage, during treatment and/or 41-;

in use, including motor fuel and still more particularly unsaturatedgasolines as cracked gasoline, polymer gasoline, etc., aviationgasoline, jet fuel, diesel oil, heater oil, mineral oil, lubricatingoil, fuel oil, drying oil, greases,

waxes, rubber, edible fats and oils, forage crops, monomers includingstyrene, butadiene, ;i sop renje,- acetylenes, etc., various unsaturatedalcohols, jacids, ketones,' etc. .These materials are adversely atfectedby. oxygen, with the resultant formation of "undesirable :gum,discoloration,

rancidity or other deleterious reaction products;

tion of fatty materials, including edible fats and oils, which may be ofanimal, vegetable or mineral origin and which tend to become rancid,especially during long periods of storage prior to use. Typicalrepresentatives of I the edible fats and oils include linseed oil,menhaden oil,

cod liver oil, castor oil/oliverfloilll rapeseed oil, coconut oil, palmoil, corn oil, sesame oil, peanut oil, babassu oil, butter, fat, lard,beef tallow, etc. It is understood that other oils and fats may betreated within the scope of the present invention, including oils andfats which previously have been subjected to various treatments such ashydrogenation, blowing with air, heat treatment, etc.

In another embodiment-the present invention may be applied to thetreatment of crops. by ,dusting or spraying in order to preserve foodaccessory factors such as carotene, vitamins, various fatty acids,alcohols, etc. In still another embodiment the present invention may beused for the stabilization of solid food products by dusting, spraying,injecting, soaking, etc. In still another embodiment the inhibitor maybe incorporated in materials which contact food products as, forexample, paraflin wax used to coat containers for food products,cardboard or other paper products used for packaging food products, etc.

In one embodiment the present invention relates to a method ofstabilizing an organic material against deterioration which comprisesincorporating therein an inwhere R is selected from the group consistingof hydrogen, hydrocarbon and substituted hydrocarbon groups.

.an indane' having a hydroxy group in the 4-position and eithera hydroxyor ether in the 7-position. Referring to the general formulahereinbefore set forth, where R is hydrogen, the inhibitor comprises a4,7-dihydroxyindane.

Where R in the above general formula is hydrocarbon group, it may beselected from such groups as alkyl, alkenyl, cycloalkyl,cycloalkylalkyl, alkylcycloalkyl, aryl, aralkyl, alkaryl,'etc. Where.R'is a substituted hydrocarbon group, it may comprise .the groupsrecited above also containing oxygen, nitrogen and/or sulfur.

Where R is an alkyl group, the inhibitor will comprise a4-hydroxy-7-alkoxyindane and includes such compounds as4-hydroxy-7-methoxyindane, 4-hydroxy-7-ethoxyindane,4-hydroxy-7-propoxyindane, 4- hydr'oxy-7- butoxyindane, 4-hydroxyJ-pentoxyindane, 4-hydroxy-7-hexoxyindane; etc. Where R is anarylgroup the cornpoundwill comprise a 4-hydroxy-7-phenoxyindan and includesuch compounds as 4-hydroxy-7-toloxyindane 4-hydroXy-7-xyloxyindane,etc. Where R is an aralkyl group, the compound will be4-hydroxy-7-benzyloxyindane, 4 hydroxy-7-phenethyloxyindane, etc.

It is-apparent that numerous compounds may be prepared and utilized inaccordancefwith the present inven- J tion. However, all these compoundsare not necessarily The invention is particularly applicable tothe'stabilizaequivalent and may be of different effectiveness in thesame or different substrate. It.also is understood that a mixture ofisomers may be used in order to, eliminate the necessity ofseparatingthe'sarne' In somefca sesja'lniix 'ture of two or moredifferent inhibitor compounds maybe m y 1 i i, f' fl 1.

The inhibitor Cam anile of" the present invention generally isincorporated in the organic material tobe s tabi lized in an amount ofnot above about 2% and .llsually in an amount within the range of fromabout 0. 000 l to about 1% by weight. When used inedible fats and oils,it is understoodthat the inhibitor compound'mayjbe utilized inconjunction with 'synergists suchas citric acid, phosphoric acid,ascorbic acid, etc., and/or combination with other inhibitors and/ orother compounds added for specific purposes.

tions, it is understood that the inhibitor compound may be, utilized inconjunction with other additives which may be incorporated in thehydrocarbon fraction asj'fo'rexample, dyes, synergists,metal'deactivators, antiknock agents, rust inhibitors, etc, Theinhibitor of the present invention may be utilized as such or in asuitable solvent, including hydrocarbons, alcohols, glycols, ethers,ketones,

etc. When desired, theiinhibitor compound may be marketed as a solutionalong 'with one or more other additives to be incorporated in theorganicmaterial.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

Example I The lard used in this example had a normal stability period of4 hours as determined by the Swift test. This test is described indetail in the article by A. E. King, H. L. Roschen and W. H. Irwin,which appeared in Oil and Soap, vol. X, No. 6, pages -109 (1933), andmodified as described in the articles by R. W. Reimenschneider, J. Turerand R. M. Spec, which appeared in Oil and Soap, pages 169-171 (1943). Ingeneral this When used in hydrocarbon. frac- 3 test-comprises bubblingairthrough a sampleof lard and determining rancidity organolepticallyand by peroxide numbers. The result of these tests is reported as A. O.M.

"stability period, which is the-number of-hours required to reach aperoxide number of-20.

' 0.02% by weightof 4,7-dihydroxyindane was incorporated in a sampledthe lard, and this served to increase the stability period thereof to'59 hours.

Example II To'anothersam'ple of the-lard'described in Example I, 'O;02%'by weight of 4-hydroxy-7-methoxyindane was added. 'This served toincrease the 'induction period'of the lard to 26 hours.

Example 111 i In contrast to the'4,7-dihydroxyindane ofExample I, andthe 4-hydroxy7-methoxyindane ofExample II, 0.02% by weight of4'-hydroxyindane was added to another sample of the lard described inExarnple I. This served to increase the stability period of the lard .toonly 5.5 hours. This example illustrates the unexpectedly higherpotencies obtained by the dihydroxy or hydroxy methoxyindanes.

'We claim as our invention: I

1. Method of stabilizing fatty material against deterioration whichcomprises incorporating therein an inhibitor having the following.general formula:

koxyindane.

Alfatty. material subject to deterioration in storage containingasan-additive to retarddeterioration a stabilizing amount of aninhibitorhaving the following general formula:

where R- is selected from the group consisting of hydrogen andhydrocarbon groups.

6. A fatty material subject to deterioration containing a stabilizingamount of 4,7-dihydroxyindane.

7. A fatty material subject to oxidative deterioration containing astabilizing amount of a 4-hydroxy-7-alkoxyindane.

8. Fatty material subject to rancidity containing, as an inhibitor toretard said rancidity, from about 0.0001% to about 1'%"by'weight of4,7-dihydroxyindane.

9. Fatty material'subje'ct to rancidity containing, as an inhibitor-toretard said rancidity, from about 0.0001% to about 1% by weight of4=hydroXy-7-methoxyindane.

10. Lard normally tending to become rancid containing from about0.'O001% to about 1% by weight of 4,7- dihydroxyindane.

11. Lard tending to deteriorate .in storage containing a stabilizingamount of aninhibitor'having the following general formula:

where Ris selected fro'ni the group consisting of hydrogen andhydrocarbon groups.

12. Lard tendingto deteriorate in" st'or'age containingastabilizingamount bf aninhibitor having the following general formula:

where R is an alkyl group.

References Cited 'in' the 1 file of this patent UNITED STATES PATENTS2,110,950 Burk et a1 Mar. 15,- 1938 2 ,176,883 -Fisher Oct. 24, 19392,670,340 Kehe Feb. 23, 1954

1. METHOD OF STABILIZING FATTY MATERIAL AGAINST DETERIORATION WHICHCOMPRISES INCORPORATING THEREIN AN INHIBITOR HAVING THE FOLLOWINGGENERAL FORMULA: